EP2711382B1 - Difluoro benzotriazolyl solar cell material and preparation method and use thereof - Google Patents
Difluoro benzotriazolyl solar cell material and preparation method and use thereof Download PDFInfo
- Publication number
- EP2711382B1 EP2711382B1 EP11872591.0A EP11872591A EP2711382B1 EP 2711382 B1 EP2711382 B1 EP 2711382B1 EP 11872591 A EP11872591 A EP 11872591A EP 2711382 B1 EP2711382 B1 EP 2711382B1
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- EP
- European Patent Office
- Prior art keywords
- solar cell
- cell material
- organic
- difluoro
- palladium
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- 239000000463 material Substances 0.000 title claims description 71
- -1 Difluoro benzotriazolyl Chemical group 0.000 title claims description 42
- 238000002360 preparation method Methods 0.000 title description 12
- 238000006243 chemical reaction Methods 0.000 claims description 42
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000005859 coupling reaction Methods 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229940126062 Compound A Drugs 0.000 claims description 11
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- SYKXNRFLNZUGAJ-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SYKXNRFLNZUGAJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000012964 benzotriazole Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- XTGFEYUEWFRHTN-UHFFFAOYSA-N 10-butyl-3,7-bis(ethenyl)phenothiazine Chemical compound C=CC1=CC=C2N(CCCC)C3=CC=C(C=C)C=C3SC2=C1 XTGFEYUEWFRHTN-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- SGNLGWHGBWHFHP-UHFFFAOYSA-N 3,7-bis(ethenyl)-10-icosylphenothiazine Chemical compound C=CC1=CC=C2N(CCCCCCCCCCCCCCCCCCCC)C3=CC=C(C=C)C=C3SC2=C1 SGNLGWHGBWHFHP-UHFFFAOYSA-N 0.000 description 1
- ZFAUZAPQOGWZJH-UHFFFAOYSA-N 3,7-bis(ethenyl)-10-octylphenothiazine Chemical compound C=CC1=CC=C2N(CCCCCCCC)C3=CC=C(C=C)C=C3SC2=C1 ZFAUZAPQOGWZJH-UHFFFAOYSA-N 0.000 description 1
- OVUVZLHNGJYTAD-UHFFFAOYSA-N 3,7-bis(ethenyl)-10-tetradecylphenothiazine Chemical compound C=CC1=CC=C2N(CCCCCCCCCCCCCC)C3=CC=C(C=C)C=C3SC2=C1 OVUVZLHNGJYTAD-UHFFFAOYSA-N 0.000 description 1
- JNIGPNKLZXHUSH-UHFFFAOYSA-N 4,7-bis(5-bromothiophen-2-yl)-2-dodecyl-5,6-difluorobenzotriazole Chemical compound FC=1C(F)=C(C=2SC(Br)=CC=2)C2=NN(CCCCCCCCCCCC)N=C2C=1C1=CC=C(Br)S1 JNIGPNKLZXHUSH-UHFFFAOYSA-N 0.000 description 1
- YREZIXGSZIMSOA-UHFFFAOYSA-N 4,7-bis(5-bromothiophen-2-yl)-5,6-difluoro-2-icosylbenzotriazole Chemical compound FC=1C(F)=C(C=2SC(Br)=CC=2)C2=NN(CCCCCCCCCCCCCCCCCCCC)N=C2C=1C1=CC=C(Br)S1 YREZIXGSZIMSOA-UHFFFAOYSA-N 0.000 description 1
- BYDFVKSTXQHQKH-UHFFFAOYSA-N 4,7-bis(5-bromothiophen-2-yl)-5,6-difluoro-2-methylbenzotriazole Chemical compound FC=1C(F)=C(C=2SC(Br)=CC=2)C2=NN(C)N=C2C=1C1=CC=C(Br)S1 BYDFVKSTXQHQKH-UHFFFAOYSA-N 0.000 description 1
- YYYNBJKAYUCPRB-UHFFFAOYSA-N 4,7-bis(5-bromothiophen-2-yl)-5,6-difluoro-2-octylbenzotriazole Chemical compound FC=1C(F)=C(C=2SC(Br)=CC=2)C2=NN(CCCCCCCC)N=C2C=1C1=CC=C(Br)S1 YYYNBJKAYUCPRB-UHFFFAOYSA-N 0.000 description 1
- NYTCBZMXAKWIPP-UHFFFAOYSA-N 4-(5-bromothiophen-2-yl)-5,6-difluoro-2h-benzotriazole Chemical compound FC=1C(F)=CC2=NNN=C2C=1C1=CC=C(Br)S1 NYTCBZMXAKWIPP-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/36—Oligomers, i.e. comprising up to 10 repeat units
- C08G2261/364—Oligomers, i.e. comprising up to 10 repeat units containing hetero atoms
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
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- C08G2261/413—Heck reactions
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- C—CHEMISTRY; METALLURGY
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- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
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- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/542—Dye sensitized solar cells
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Definitions
- the present disclosure relates to a field of solar cell materials, and more particularly relates to a difluoro benzotriazolyl solar cell material, a preparation method and a use thereof.
- Benzotriazolyl materials have been described inter alia in Zhenhua Zhang et al, Applied Polymer Science, 2010, 2534-2542 .
- the present disclosure is directed to a difluoro benzotriazolyl solar cell with a high energy conversion efficiency.
- a difluoro benzotriazolyl solar cell material is represented by formula (I), wherein R 1 and R 2 are C 1 to C 20 alkyl, n is an integer from 10 to 50, preferably 30 to 40.
- the present disclosure is also directed to a method of preparing the difluoro benzotriazolyl solar cell material, which includes the following steps:
- the method of preparing the difluoro benzotriazolyl solar cell material further includes:
- the catalyst in step S2 is organic palladium, or the catalyst is a mixture of organic palladium and organic phosphorus ligand.
- a molar ratio between the organic palladium and the compound A is 1:20 to 1:100.
- the organic palladium is at least one selected from the group consisting of bis(triphenylphosphine) palladium(II) dichloride, tetrakis(triphenylphosphine)platinum, and palladium acetate; the organic phosphorus ligand is tri-o-tolyl phosphine.
- the organic solvent in step S2 is at least one selected from the group consisting of toluene, N, N-dimethylformamide, and tetrahydrofuran.
- a reaction temperature of the Heck coupling reaction is 90°C to 120°C
- a reaction time of the Heck coupling reaction is 48 to 72 hours.
- the present invention is further directed to a use of the difluoro benzotriazolyl solar cell material in an organic solar cell.
- the 1, 2, 3-benzotriazole solar cell material contains two fluorine atoms, the HOMO energy level of the material is reduced by 0.11eV, while the fluorine-substituted 1, 2, 3-benzotriazole has two imido groups with electron-withdrawing ability; the fluorine-substituted 1, 2, 3-benzotriazole is a heterocyclic compound with a strong electron-withdrawing ability, and an alkyl chain can be easily introduced to the N-position of the N-H bond of the benzotriazole.
- the functional group of the alkyl chain can improve the solar energy conversion efficiency, thus solving the low efficiency problem of solar cells made of the solar cell material.
- the functional group of the alkyl chain can adjust the solubility of the difluoro benzotriazolyl solar cell material, so that the solar cell material is conducive to film forming processing, and its application range in the solar cell material or in the field of solar cell is expanded.
- the present disclosure provides a difluoro benzotriazolyl solar cell material represented by formula (I): where R 1 and R 2 are C 1 to C 20 alkyl, n is an integer from 10 to 50, preferably from 30 to 40.
- a method of preparing the difluoro benzotriazolyl solar cell material includes the following steps:
- step S2 Methanol is added to the reaction solution of step S2, and the reaction solution is then precipitated, filtered by a Soxhlet extractor, and extracted and precipitated successively with methanol and n-hexane extraction for 24 hours.
- the reaction solution is then extracted and precipitated using chloroform as a solvent until the reaction solution is colorless.
- the chloroform solution is collected and rotary evaporated to obtain a red powder, which is then dried under vacuum at a temperature of 50°C for 24 hours to obtain a purified difluoro benzotriazolyl solar cell material.
- the catalyst is organic palladium, or the catalyst is a mixture of organic palladium and organic phosphorus ligand.
- a molar ratio between the organic palladium and the compound A is 1:20 to 1:100.
- the organic palladium is at least one selected from the group consisting of bis(triphenylphosphine) palladium(II) dichloride, tetrakis(triphenylphosphine)platinum, and palladium acetate.
- the organic phosphorus ligand is tri-o-tolyl phosphine, in the mixture of organic palladium and organic phosphorus ligand, a molar ratio between the organic palladium and the organic phosphorus ligand is 1:3 to 1:6.
- the organic solvent is at least one selected from the group consisting of toluene, N, N-dimethylformamide, and tetrahydrofuran.
- a reaction temperature of the Heck coupling reaction is from 90°C to 120°C, a reaction time of the Heck coupling reaction is 48 to 72 hours.
- the 1,2,3-benzotriazole solar cell material contains two fluorine atoms, the HOMO energy level of the material is reduced by 0.11eV, while the fluorine-substituted 1,2,3-benzotriazole has two imido groups with an electron-withdrawing ability; the fluorine-substituted 1, 2, 3-benzotriazole is a heterocyclic compound with a strong electron-withdrawing ability, and an alkyl chain can be easily introduced to the N-position of the N-H bond of the benzotriazole.
- the functional group of the alkyl chain can improve the solar energy conversion efficiency, thus solving the low efficiency problem of solar cells made of the solar cell material.
- the functional group of the alkyl chain can adjust the solubility of the difluoro benzotriazolyl solar cell material, so that the solar cell material is conducive to film forming processing, and its application range in the solar cell material or in the field of solar cell is expanded.
- the preparation method of the present disclosure employs a relatively simple synthetic route, thereby simplifying the process; the manufacturing cost is reduced due to the inexpensive and readily available materials.
- difluoro benzotriazolyl solar cell material can be applied to the active layer of the organic solar cell.
- the monomer of the compound A can be purchased from the market, the monomer of the compound B can be prepared according to the reference ( J. Am. Chem. Soc. 2011, 133, 4625 ) or purchased from the market.
- the difluoro benzotriazolyl solar cell material of this example was poly ⁇ N-n-octyl-3, 7 - divinyl phenothiazine-co-2-n-octyl-4, 7 - dithienyl -5,6 - difluorophenyl-benzotriazole ⁇ , where R 1 is n-octyl, R 2 is n-octyl, n is 40.
- the material had a following formula:
- the preparation of the solar cell material included the steps of:
- N-n-octyl-3,7 - divinyl phenothiazine (109mg, 0.3mmol)
- 2 - n-octyl-4,7 - bis (5 - bromo-thienyl) -5,6 - difluoro-1, 2, 3 - benzotriazole (176.8 mg, 0.3 mmol)
- palladium acetate 10.1 mg, 0.015 mmol
- tri-o-methoxy phosphorus 3 mg
- reaction solution 40mL of methanol was added to the flask, the reaction solution was precipitated, filtrated by a Soxhlet extractor, then was successively extracted and precipitated with methanol and hexane for 24 hours. The reaction solution is then extracted and precipitated using chloroform as a solvent until the reaction solution is colorless.
- the chloroform solution was collected and rotary evaporated to obtain a red powder, which was then dried under vacuum at a temperature of 50°C for 24 hours to obtain the poly ⁇ N-n-octyl-3,7 - divinyl phenothiazine-co-2-n-octyl-4 ,7 - dithienyl -5,6 - difluorophenyl-benzotriazole ⁇ with a yield of 57%.
- the difluoro benzotriazolyl solar cell material of this example was poly ⁇ N-methyl-3, 7 - divinyl phenothiazine-co-2-n-eicosyl-4, 7 - dithienyl -5,6 - difluorophenyl-benzotriazole ⁇ , where R 1 is methyl, R 2 is n-eicosyl, n is 36.
- the material had a following formula:
- the preparation of the solar cell material included the steps of:
- N-methyl-7 - divinyl phenothiazine (53 mg, 0.2mmol) and 2 - eicosyl -4, 7 - bis (5 - bromo-thienyl) -5,6 - difluoro-1, 2, 3 -benzotriazole (151.4 mg, 0.2 mmol) were added to a flask containing 15mL of toluene and were dissolved to form a solution. The flask was evacuated to remove oxygen by introducing argon.
- the difluoro benzotriazolyl solar cell material of this example was poly ⁇ N-n-eicosyl -3, 7 - divinyl phenothiazine-co-2-methyl-4,7 - dithienyl -5,6 - difluoro-triazole ⁇ , where R 1 is n-eicosyl, R 2 is methyl, n is 30.
- the material had a following formula:
- the preparation of the solar cell material included the steps of:
- N-n-eicosyl -3, 7 - divinyl phenothiazine (160 mg, 0.3 mmol) and 2 - methyl -4, 7 - bis (5 - bromo-thienyl) -5,6 - difluoro-1, 2, 3 -benzotriazole (147.3 mg, 0.3 mmol) were added to a 50mL two-necked flask containing 15mL of tetrahydrofuran. A mixture of nitrogen and argon was introduced into the two-necked flask to exhaust air for approximately 20 minutes.
- FIG. 2 shows an ultraviolet visible absorption spectrum of poly ⁇ N-n-eicosyl -3, 7 - divinyl phenothiazine-co-2-methyl-4, 7 - dithienyl -5,6 - difluoro-triazole ⁇ prepared according to the example 3, it can be seen from the FIG. 2 that the conjugated polymer has a strong absorption peak at about 600 nm.
- the difluoro benzotriazolyl solar cell material of this example was poly ⁇ N-tetradecyl -3, 7 - divinyl phenothiazine-co-2-n-decyl-4 ,7 - dithienyl -5,6 - difluoro-triazole ⁇ , where R 1 is n-tetradecyl, R 2 is N-decyl, n is 10.
- the material had a following formula:
- the preparation of the solar cell material included the steps of:
- N-tetradecyl -3, 7 - divinyl phenothiazine (78.6mg, 0.2mmol) and 2 - n-decyl -4 7 - bis (5 - bromo-thienyl) -5,6 - difluoro-1, 2, 3 - benzotriazole (135mg, 0.2 mmol) were added to a flask containing 15mL of toluene and dissolved to form a solution. The flask was evacuated to remove oxygen by introducing argon.
- the difluoro benzotriazolyl solar cell material of this example was poly ⁇ N-n-butyl-3, 7 - divinyl phenothiazine-co-2-n-dodecyl-4, 7 - dithienyl -5,6 - difluoro-triazole ⁇ , where R 1 is n-butyl, R 2 is n-dodecyl, n is 50.
- the material had a following formula:
- the preparation of the solar cell material included the steps of:
- N-n-butyl-3, 7 - divinyl phenothiazine (93 mg, 0.3 mmol) and 2 - dodecyl -4, 7 - bis (5 - bromo-thienyl) -5,6 - difluoro-1, 2, 3 - benzotriazole (192.9 mg, 0.3 mmol) were added to a 50mL two-necked flask containing 15mL of tetrahydrofuran. A mixture of nitrogen and argon was introduced into the two-necked flask to exhaust air for approximately 20 minutes.
- a organic solar cell of the present example employed poly ⁇ N-n-eicosyl -3, 7 - divinyl phenothiazine-co-2-methyl-4, 7 - dithienyl -5,6 - difluoro-triazole ⁇ (i.e. DFBTz-PTZ3) prepared according to Example 3 as an electron donor material for an active layer.
- the organic solar cell device includes a glass substrate 11, a transparent anode 12, an intermediate auxiliary layer 13, an active layer14, and a cathode 15, which are laminated in that order.
- the transparent anode 12 can be made of indium tin oxide (abbreviation as ITO), preferably the indium tin oxide with a sheet resistance of 10-20 ⁇ /sq.
- the intermediate auxiliary layer 13 is made of a composite of poly 3, 4-ethylenedioxythiophene and poly styrene sulfonate (abbreviation as PEDOT: PSS).
- the active layer 14 includes an electron donor material and an electron acceptor material.
- the electron donor material is the polymer obtained from the example 1 (i.e.
- the cathode 15 can be aluminum electrode or double-layer metal electrode, such as Ca/Al or Ba/Al and so on, the thickness of the cathode 15 is preferably 170nm, 30mm, 130nm or 60nm.
- the glass substrate 11 can be used as a bottom layer.
- the ITO glass is cleaned by ultrasonic and treated with oxygen-Plasma, and then spin-coated with the intermediate auxiliary layer 13.
- the polymer obtained from the Example 1 and the electron acceptor material are mixed and coated on the intermediate auxiliary layer 13 to form the active layer 14, and then the cathode 15 is deposited on the active layer 14 by vacuum deposition techniques, such that the organic solar cell device is obtained.
- the organic solar cell is then heated for 4 hours at 110°C under an airtight condition, and cooled to room temperature.
- the thickness of the Al layer of the cathode 15 is 170nm.
- the light passes through the glass substrate 11 and the ITO electrode 12, then the light energy is absorbed by the hole-conduction type electroluminescent material of the active layer 14, and excitons are generated.
- the excitons then migrate to an interface between the electron donor and acceptor materials, and transfer the electrons to the electron acceptor material, such as PCBM, therefore the charges are separated, thereby forming the free carriers, i.e. the free electrons and the holes.
- the free electrons are transferred to the cathode along the electron acceptor material and are collected by the cathode, the free holes are transferred along the electron donor material and are collected by the anode, thereby forming the photocurrent and photovoltage, and photoelectric conversion is achieved.
- the solar cell When a load 16 is connected, the solar cell is capable of supplying power. Since the hole-conduction type electroluminescent material has a wide spectral response range, the light energy is fully utilized to obtain much higher photoelectric conversion efficiency, and the power generation capacity of the organic solar cell is increased. In addition, this type of the organic material can also reduce the weight of the organic solar cell, it can be made by spin coating technology for mass production.
- the energy conversion efficiency of the bulk-heterojunction solar cell based on the DFBTz-PTZ3 as the electron donor material is 3.2%, where AM means the air mass, which is represented by the ratio between the optical path-length of solar beam through the atmosphere relative to the optical path-length of the solar beam at zenith reaching to the sea level.
- the AM 1.5 condition means the irradiance and spectral distribution for calibrating and testing the terrestrial solar cell; the total solar irradiance is 1000 Watts per square meter, the measured temperature of the solar cell is 25 °C; the standard is enacted by the International Electrotechnical Commission, which is the currently standard in our country, specifically, one standard solar corresponds to the irradiation strength of the AM1.5G standard light source, AM1.5G represents the sunlight with a 48° zenith angle (the angle between the incident light from the incident light source and the normal of the earth), the light intensity is 1000 W/m 2 (i.e. AM 1.5, 100 mW/cm 2 illumination).
Description
- The present disclosure relates to a field of solar cell materials, and more particularly relates to a difluoro benzotriazolyl solar cell material, a preparation method and a use thereof.
- The preparation of solar cell with low price and high performance using cheap materials has always been a hotspot and difficulty in the field of solar photovoltaic research. The current silicon cell used for ground is limited mainly because of the complex production process and the high cost. In order to reduce the cost of the cell and expand its application range, people have been looking for a new solar cell material for a long time. The organic semiconductor material has gained lots of concern due to the advantages of readily accessible raw material, inexpensive, simple preparation process, good environmental stability and photovoltaic effect and so on. Since N. S. Sariciftci, et al reported the phenomenon of photoinduced electron transferring between conjugated organic semiconductor materials and C60 on the SCIENCE in 1992 (N. S Sariciftci, L. Smilowitz, A. J. Heeger, et al. Science, 1992, 258, 1474), numerous researches have been invested into the polymer solar cell. Although it has been rapidly developed, the conversion efficiency of the polymer solar cell is still much lower than that of the inorganic solar cell.
- Benzotriazolyl materials have been described inter alia in Zhenhua Zhang et al, Applied Polymer Science, 2010, 2534-2542.
- The present disclosure is directed to a difluoro benzotriazolyl solar cell with a high energy conversion efficiency.
-
- The present disclosure is also directed to a method of preparing the difluoro benzotriazolyl solar cell material, which includes the following steps:
- step S1, providing compounds A and B represented by the following formulas,
-
step 2, adding the compound A and the compound B to an organic solvent containing a catalyst according to a molar ratio of 1:1 in an oxygen-free environment, performing a Heck coupling reaction for 24 to 96 hours at a temperature from 70°C to 130°C, then obtaining the difluoro benzotriazolyl solar cell material represented by formula (I): - The method of preparing the difluoro benzotriazolyl solar cell material further includes:
- step S3, purifying the difluoro benzotriazolyl solar cell material obtained from step S2.
- In the method of preparing the difluoro benzotriazolyl solar cell material, the catalyst in step S2 is organic palladium, or the catalyst is a mixture of organic palladium and organic phosphorus ligand. A molar ratio between the organic palladium and the compound A is 1:20 to 1:100. The organic palladium is at least one selected from the group consisting of bis(triphenylphosphine) palladium(II) dichloride, tetrakis(triphenylphosphine)platinum, and palladium acetate; the organic phosphorus ligand is tri-o-tolyl phosphine.
- The organic solvent in step S2 is at least one selected from the group consisting of toluene, N, N-dimethylformamide, and tetrahydrofuran.
- Preferably, in step S2, a reaction temperature of the Heck coupling reaction is 90°C to 120°C, a reaction time of the Heck coupling reaction is 48 to 72 hours.
- The present invention is further directed to a use of the difluoro benzotriazolyl solar cell material in an organic solar cell.
- In the difluoro benzotriazolyl solar cell material, since the 1, 2, 3-benzotriazole solar cell material contains two fluorine atoms, the HOMO energy level of the material is reduced by 0.11eV, while the fluorine-substituted 1, 2, 3-benzotriazole has two imido groups with electron-withdrawing ability; the fluorine-substituted 1, 2, 3-benzotriazole is a heterocyclic compound with a strong electron-withdrawing ability, and an alkyl chain can be easily introduced to the N-position of the N-H bond of the benzotriazole. The functional group of the alkyl chain can improve the solar energy conversion efficiency, thus solving the low efficiency problem of solar cells made of the solar cell material. In addition, the functional group of the alkyl chain can adjust the solubility of the difluoro benzotriazolyl solar cell material, so that the solar cell material is conducive to film forming processing, and its application range in the solar cell material or in the field of solar cell is expanded.
-
-
FIG. 1 is a flow chart of the method of preparing a difluoro benzotriazolyl solar cell material according to the present disclosure; -
FIG. 2 is an ultraviolet visible absorption spectrum of poly{N-n-eicosyl alkyl-3, 7 - divinyl phenothiazine-co-2-methyl-4 ,7 - dithienyl -5,6 - difluorophenyl-benzotriazole} prepared according to Example 3; and -
FIG. 3 is a schematic structure view of the organic solar cell according to Example 4. -
- Referring to
FIG. 1 , a method of preparing the difluoro benzotriazolyl solar cell material includes the following steps: - Step S1, a compound A and a compound B represented by the following formulas are provided, respectively.
- Step S2, in an oxygen-free environment (e.g., an environment composed of nitrogen, argon, or a mixture of nitrogen and argon, etc.), the compound A and the compound B are added to an organic solvent containing a catalyst according to a molar ratio of 1:1. Then a Heck coupling reaction is performed for 24 to 96 hours at a temperature from 70°C to 130°C. A reaction solution containing the product, i.e. the difluoro benzotriazolyl solar cell material represented by the formula (I), is obtained:
- Step S3, the product obtained in step S2 is purified according to the following procedures:
- Methanol is added to the reaction solution of step S2, and the reaction solution is then precipitated, filtered by a Soxhlet extractor, and extracted and precipitated successively with methanol and n-hexane extraction for 24 hours. The reaction solution is then extracted and precipitated using chloroform as a solvent until the reaction solution is colorless. The chloroform solution is collected and rotary evaporated to obtain a red powder, which is then dried under vacuum at a temperature of 50°C for 24 hours to obtain a purified difluoro benzotriazolyl solar cell material.
- In step S2 of the preparation method, the catalyst is organic palladium, or the catalyst is a mixture of organic palladium and organic phosphorus ligand. A molar ratio between the organic palladium and the compound A is 1:20 to 1:100. The organic palladium is at least one selected from the group consisting of bis(triphenylphosphine) palladium(II) dichloride, tetrakis(triphenylphosphine)platinum, and palladium acetate. The organic phosphorus ligand is tri-o-tolyl phosphine, in the mixture of organic palladium and organic phosphorus ligand, a molar ratio between the organic palladium and the organic phosphorus ligand is 1:3 to 1:6.
- The organic solvent is at least one selected from the group consisting of toluene, N, N-dimethylformamide, and tetrahydrofuran.
- Preferably, in step S2, a reaction temperature of the Heck coupling reaction is from 90°C to 120°C, a reaction time of the Heck coupling reaction is 48 to 72 hours.
- In the difluoro benzotriazolyl solar cell material, since the 1,2,3-benzotriazole solar cell material contains two fluorine atoms, the HOMO energy level of the material is reduced by 0.11eV, while the fluorine-substituted 1,2,3-benzotriazole has two imido groups with an electron-withdrawing ability; the fluorine-substituted 1, 2, 3-benzotriazole is a heterocyclic compound with a strong electron-withdrawing ability, and an alkyl chain can be easily introduced to the N-position of the N-H bond of the benzotriazole. The functional group of the alkyl chain can improve the solar energy conversion efficiency, thus solving the low efficiency problem of solar cells made of the solar cell material. In addition, the functional group of the alkyl chain can adjust the solubility of the difluoro benzotriazolyl solar cell material, so that the solar cell material is conducive to film forming processing, and its application range in the solar cell material or in the field of solar cell is expanded.
- Furthermore, the preparation method of the present disclosure employs a relatively simple synthetic route, thereby simplifying the process; the manufacturing cost is reduced due to the inexpensive and readily available materials.
- The foregoing difluoro benzotriazolyl solar cell material can be applied to the active layer of the organic solar cell.
- For a better understanding of the present disclosure, the technical solution of the present disclosure is further illustrated by the specific examples and drawings, which includes the materials preparation and device fabrication. However, the specific examples are not intended to limit the scope of the present disclosure. The monomer of the compound A can be purchased from the market, the monomer of the compound B can be prepared according to the reference ( J. Am. Chem. Soc. 2011, 133, 4625 ) or purchased from the market.
-
- The preparation of the solar cell material included the steps of:
-
- N-n-octyl-3,7 - divinyl phenothiazine (109mg, 0.3mmol), 2 - n-octyl-4,7 - bis (5 - bromo-thienyl) -5,6 - difluoro-1, 2, 3 - benzotriazole (176.8 mg, 0.3 mmol), palladium acetate (10.1 mg, 0.015 mmol), and tri-o-methoxy phosphorus (3 mg) were added to a flask containing 12mL of N, N-dimethylformamide and were dissolved to form a solution. After the nitrogen was sufficiently introduced to the flask to exhaust the air for 30 min, a Heck coupling reaction was performed for 48 hours at a temperature of 120°C with stirring, the polymerization reaction was stopped after cooling, and a reaction solution was obtained.
- 40mL of methanol was added to the flask, the reaction solution was precipitated, filtrated by a Soxhlet extractor, then was successively extracted and precipitated with methanol and hexane for 24 hours. The reaction solution is then extracted and precipitated using chloroform as a solvent until the reaction solution is colorless. The chloroform solution was collected and rotary evaporated to obtain a red powder, which was then dried under vacuum at a temperature of 50°C for 24 hours to obtain the poly {N-n-octyl-3,7 - divinyl phenothiazine-co-2-n-octyl-4 ,7 - dithienyl -5,6 - difluorophenyl-benzotriazole} with a yield of 57%.
- Test results: Molecular weight (GPC, THF, R. I): Mn =31.9 kDa, Mw/Mn =2.2.
-
- The preparation of the solar cell material included the steps of:
-
- N-methyl-7 - divinyl phenothiazine (53 mg, 0.2mmol) and 2 - eicosyl -4, 7 - bis (5 - bromo-thienyl) -5,6 - difluoro-1, 2, 3 -benzotriazole (151.4 mg, 0.2 mmol) were added to a flask containing 15mL of toluene and were dissolved to form a solution. The flask was evacuated to remove oxygen by introducing argon. After 5mg of bis triphenylphosphine palladium dichloride was added to the flask, a Heck coupling reaction was performed for 72 hours at a temperature of 100°C with stirring, the polymerization reaction was stopped after cooling, and a reaction solution was obtained.
- 50mL of methanol was added to the flask, the reaction solution was precipitated, filtrated by a Soxhlet extractor, then was successively extracted and precipitated with methanol and hexane for 24 hours. The reaction solution is then extracted and precipitated using chloroform as a solvent until the reaction solution is colorless. The chloroform solution was collected and rotary evaporated to obtain a red powder, which was then dried under vacuum at a temperature of 50°C for 24 hours to obtain the poly {N-methyl-3,7 - divinyl phenothiazine-co-2-n-eicosyl-4, 7 - dithienyl -5,6 - difluorophenyl-benzotriazole} with a yield of 57%.
- Test results: Molecular weight (GPC, THF, R. I): Mn =30.8 kDa, Mw/Mn =2.2.
-
- The preparation of the solar cell material included the steps of:
-
- N-n-eicosyl -3, 7 - divinyl phenothiazine (160 mg, 0.3 mmol) and 2 - methyl -4, 7 - bis (5 - bromo-thienyl) -5,6 - difluoro-1, 2, 3 -benzotriazole (147.3 mg, 0.3 mmol) were added to a 50mL two-necked flask containing 15mL of tetrahydrofuran. A mixture of nitrogen and argon was introduced into the two-necked flask to exhaust air for approximately 20 minutes. After 17mg of palladium tetrakis(triphenylphosphine) was added to the flask and approximately 10 minutes of exhausting air by the mixture of nitrogen and argon, a Heck coupling reaction was performed for 60 hours at a temperature of 90°C with stirring, the polymerization reaction was stopped after cooling, and a reaction solution was obtained.
- 40mL of methanol was added to the flask, the reaction solution was precipitated, filtrated by a Soxhlet extractor, then was successively extracted and precipitated with methanol and hexane for 24 hours. The reaction solution is then extracted and precipitated using chloroform as a solvent until the reaction solution is colorless. The chloroform solution was collected and rotary evaporated to obtain a red powder, which was then dried under vacuum at a temperature of 50°C for 24 hours to obtain the poly {N-n-eicosyl -3, 7 - divinyl phenothiazine-co-2-methyl-4, 7 - dithienyl -5,6 - difluoro-triazole} with a yield of 50%.
- Test results: Molecular weight (GPC, THF, R. I): Mn =26.0 kDa, Mw/Mn =2.2.
-
FIG. 2 shows an ultraviolet visible absorption spectrum of poly {N-n-eicosyl -3, 7 - divinyl phenothiazine-co-2-methyl-4, 7 - dithienyl -5,6 - difluoro-triazole} prepared according to the example 3, it can be seen from theFIG. 2 that the conjugated polymer has a strong absorption peak at about 600 nm. -
- The preparation of the solar cell material included the steps of:
-
- N-tetradecyl -3, 7 - divinyl phenothiazine (78.6mg, 0.2mmol) and 2 - n-decyl -4 7 - bis (5 - bromo-thienyl) -5,6 - difluoro-1, 2, 3 - benzotriazole (135mg, 0.2 mmol) were added to a flask containing 15mL of toluene and dissolved to form a solution. The flask was evacuated to remove oxygen by introducing argon. After bis triphenylphosphine palladium dichloride (0.01 mmol, 7.02 mg) was added to the flask, a Heck coupling reaction was performed for 24 hours at a temperature of 130°C with stirring, the polymerization reaction was stopped after cooling, and a reaction solution was obtained.
- 50mL of methanol was added to the flask, the reaction solution was precipitated, filtrated by a Soxhlet extractor, then was successively extracted and precipitated with methanol and hexane for 24 hours. The reaction solution is then extracted and precipitated using chloroform as a solvent until the reaction solution is colorless. The chloroform solution was collected and rotary evaporated to obtain a red powder, which was then dried under vacuum at a temperature of 50°C for 24 hours to obtain the poly {N-tetradecyl -3, 7 - divinyl phenothiazine-co-2-n-decyl-4, 7 - dithienyl -5,6 - difluoro-triazole} with a yield of 48%.
- Test results: Molecular weight (GPC, THF, R. I): Mn =10.1 kDa, Mw/Mn =2.4.
-
- The preparation of the solar cell material included the steps of:
-
- N-n-butyl-3, 7 - divinyl phenothiazine (93 mg, 0.3 mmol) and 2 - dodecyl -4, 7 - bis (5 - bromo-thienyl) -5,6 - difluoro-1, 2, 3 - benzotriazole (192.9 mg, 0.3 mmol) were added to a 50mL two-necked flask containing 15mL of tetrahydrofuran. A mixture of nitrogen and argon was introduced into the two-necked flask to exhaust air for approximately 20 minutes. After palladium tetrakis(triphenylphosphine) (0.003 mmol, 3.7 mg) was added to the flask, a Heck coupling reaction was performed for 96 hours at a temperature of 70°C with stirring, the polymerization reaction was stopped after cooling, and a reaction solution was obtained.
- 40mL of methanol was added to the flask, the reaction solution was precipitated, filtrated by a Soxhlet extractor, then was successively extracted and precipitated with methanol and hexane for 24 hours. The reaction solution is then extracted and precipitated using chloroform as a solvent until the reaction solution is colorless. The chloroform solution was collected and rotary evaporated to obtain a red powder, which was then dried under vacuum at a temperature of 50°C for 24 hours to obtain the poly {N-n-butyl-3, 7 - divinyl phenothiazine-co-2-n-dodecyl-4 ,7 - dithienyl -5,6 - difluoro-triazole } with a yield of 72%.
- Test results: Molecular weight (GPC, THF, R. I): Mn =39.6 kDa, Mw/Mn =2.1.
- A organic solar cell of the present example employed poly {N-n-eicosyl -3, 7 - divinyl phenothiazine-co-2-methyl-4, 7 - dithienyl -5,6 - difluoro-triazole} (i.e. DFBTz-PTZ3) prepared according to Example 3 as an electron donor material for an active layer.
- Referring to
FIG. 3 , the organic solar cell device includes aglass substrate 11, atransparent anode 12, an intermediateauxiliary layer 13, an active layer14, and acathode 15, which are laminated in that order. Thetransparent anode 12 can be made of indium tin oxide (abbreviation as ITO), preferably the indium tin oxide with a sheet resistance of 10-20Ω/sq. The intermediateauxiliary layer 13 is made of a composite ofpoly 3, 4-ethylenedioxythiophene and poly styrene sulfonate (abbreviation as PEDOT: PSS). Theactive layer 14 includes an electron donor material and an electron acceptor material. The electron donor material is the polymer obtained from the example 1 (i.e. DFBTz- PTZ3); the electron acceptor material can be [6, 6] - phenyl - C61 - butyric acid methyl ester (abbreviation as PCBM). Thecathode 15 can be aluminum electrode or double-layer metal electrode, such as Ca/Al or Ba/Al and so on, the thickness of thecathode 15 is preferably 170nm, 30mm, 130nm or 60nm. - The
glass substrate 11 can be used as a bottom layer. In fabrication, the ITO glass is cleaned by ultrasonic and treated with oxygen-Plasma, and then spin-coated with the intermediateauxiliary layer 13. The polymer obtained from the Example 1 and the electron acceptor material are mixed and coated on the intermediateauxiliary layer 13 to form theactive layer 14, and then thecathode 15 is deposited on theactive layer 14 by vacuum deposition techniques, such that the organic solar cell device is obtained. The organic solar cell is then heated for 4 hours at 110°C under an airtight condition, and cooled to room temperature. Such an annealing process can effectively increase the arranged orderliness and regularity of each group in the molecule and the molecular chain segments, and the carrier mobility and efficiency of the transmission speed are improved, thereby improving the photoelectric conversion efficiency. In the illustrated embodiment, the thickness of the Al layer of thecathode 15 is 170nm. - Referring to the
FIG. 3 , under illumination, the light passes through theglass substrate 11 and theITO electrode 12, then the light energy is absorbed by the hole-conduction type electroluminescent material of theactive layer 14, and excitons are generated. The excitons then migrate to an interface between the electron donor and acceptor materials, and transfer the electrons to the electron acceptor material, such as PCBM, therefore the charges are separated, thereby forming the free carriers, i.e. the free electrons and the holes. The free electrons are transferred to the cathode along the electron acceptor material and are collected by the cathode, the free holes are transferred along the electron donor material and are collected by the anode, thereby forming the photocurrent and photovoltage, and photoelectric conversion is achieved. When aload 16 is connected, the solar cell is capable of supplying power. Since the hole-conduction type electroluminescent material has a wide spectral response range, the light energy is fully utilized to obtain much higher photoelectric conversion efficiency, and the power generation capacity of the organic solar cell is increased. In addition, this type of the organic material can also reduce the weight of the organic solar cell, it can be made by spin coating technology for mass production. - The photovoltaic properties of the organic solar cell of Example 6 are shown in Table 1 (Note: PCE represents the power conversion efficiency, Voc represents the open circuit voltage, Jsc represents the short circuit current, FF represents the fill factor.)
Table 1 V oc(V) J sc(mA/cm2) FF(%) PCE(%) DFBTz-PPV1/PCBM 0.70 9.39 46.7 3.1 - As can be seen from Table 1, under an illumination of AM 1.5, 100 mW/cm2, the energy conversion efficiency of the bulk-heterojunction solar cell based on the DFBTz-PTZ3 as the electron donor material is 3.2%, where AM means the air mass, which is represented by the ratio between the optical path-length of solar beam through the atmosphere relative to the optical path-length of the solar beam at zenith reaching to the sea level. The AM 1.5 condition means the irradiance and spectral distribution for calibrating and testing the terrestrial solar cell; the total solar irradiance is 1000 Watts per square meter, the measured temperature of the solar cell is 25 °C; the standard is enacted by the International Electrotechnical Commission, which is the currently standard in our country, specifically, one standard solar corresponds to the irradiation strength of the AM1.5G standard light source, AM1.5G represents the sunlight with a 48° zenith angle (the angle between the incident light from the incident light source and the normal of the earth), the light intensity is 1000 W/m2 (i.e. AM 1.5, 100 mW/cm2 illumination).
Claims (10)
- The difluoro benzotriazolyl solar cell material according to claim 1, wherein n is from 30 to 40.
- A method of preparing a difluoro benzotriazolyl solar cell material, comprising the following steps:step S1, providing compounds A and B represented by the following formulas,step 2, adding the compound A and the compound B to an organic solvent containing a catalyst according to a molar ratio of 1:1 in an oxygen-free environment, performing a Heck coupling reaction for 24 to 96 hours at a temperature from 70°C to 130°C, then obtaining the difluoro benzotriazolyl solar cell material represented by formula (I):
- The method according to claim 3 further comprising:step S3, purifying the difluoro benzotriazolyl solar cell material obtained from step S2.
- The method according to claim 3 or claim 4, wherein the catalyst in step S2 is organic palladium, or the catalyst is a mixture of organic palladium and organic phosphorus ligand.
- The method according to claim 5, wherein the organic palladium is at least one selected from the group consisting of bis(triphenylphosphine) palladium(II) dichloride, tetrakis(triphenylphosphine)platinum, and palladium acetate; the organic phosphorus ligand is tri-o-tolyl phosphine.
- The method according to claim 5, wherein a molar ratio between the organic palladium and the compound A is 1:20 to 1:100.
- The method according to claim 3 or claim 4, wherein the organic solvent in step S2 is at least one selected from the group consisting of toluene, N, N-dimethylformamide, and tetrahydrofuran.
- The method according to claim 3 or claim 4, wherein in step S2, a reaction temperature of the Heck coupling reaction is 90°C to 120°C, a reaction time of the Heck coupling reaction is 48 to 72 hours.
- A use of the difluoro benzotriazolyl solar cell material according to claim 1 in an organic solar cell.
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